PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2682–o2683.
Published online 2009 October 10. doi:  10.1107/S1600536809040616
PMCID: PMC2971323

1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–terephthalic acid–water (1/1/4)

Abstract

The asymmetric unit of the title compound, C12H14N4·C8H6O4·4H2O, consists of one half of the 1,4-bis­(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) mol­ecule, one half of the terephthalic acid (TA) mol­ecule and two water mol­ecules. Both the bib and the TA mol­ecules reside on crystallographic inversion centers, which coincide with the centroids of the respective benzene rings. The bib and the TA, together with the water mol­ecules, are linked through inter­molecular O—H(...)O, O—H(...)N and N—H(...)O hydrogen bonds, forming a three-dimensional network of stacked layers. Weak inter­molecular C—H(...)O contacts support the stability of the crystal structure.

Related literature

For general background, see: Jeffrey (1997 [triangle]). For hydrogen bonding in mol­ecular complexes of disubstituted biphenyls, see: Thaimattam et al. (1998 [triangle]). For the synthesis of the title compound, see: Ren et al. (2007 [triangle]). For related structures, see: Ren et al. (2007 [triangle], 2009 [triangle] and literature cited therein); Shang et al. (2009 [triangle]). For experimental refinement details, see: Nardelli, (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2682-scheme1.jpg

Experimental

Crystal data

  • C12H14N4·C8H6O4·4H2O
  • M r = 452.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2682-efi1.jpg
  • a = 7.9929 (13) Å
  • b = 16.847 (3) Å
  • c = 7.9615 (12) Å
  • β = 94.899 (3)°
  • V = 1068.2 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 273 K
  • 0.50 × 0.35 × 0.30 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.947, T max = 0.968
  • 5588 measured reflections
  • 2300 independent reflections
  • 832 reflections with I > 2σ(I)
  • R int = 0.075

Refinement

  • R[F 2 > 2σ(F 2)] = 0.090
  • wR(F 2) = 0.257
  • S = 0.79
  • 2300 reflections
  • 158 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.71 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT-Plus (Bruker, 1998 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809040616/si2204sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040616/si2204Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was generously supported by the National Natural Science Foundation of China (No. 20701016).

supplementary crystallographic information

Comment

Attention has recently focused on the use of supramolecular interactions such as hydrogen bonding and π–π interactions, in addition to coordinate bonds, in the controlled assembly of supramolecular architectures (Jeffrey, 1997). Hydrogen bonds often play a dominant role in crystal engineering because of their combine strength with directionality (Thaimattam, et al., 1998). On the other hand, supramolecular systems sustained by soft connections, such as hydrogen bonds, are comparatively more flexible and sensitive to the chemical environment. We described previously a number of such complexes, including the imidazole ligand, and have concluded that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism [Ren, et al. (2007, 2009 and literature cited therein); Shang et al. (2009)]. We describe herewith the synthesis and crystal structure of the title compound, (Fig. 1), namely bib.TA.4H2O (I) (bib = 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene, TA = terephthalate), which exhibits a three-dimensional hydrogen-bonded molecular architecture.

The crystal lattice contains two bib, two TA and eight lattice water molecules in the solid. The bib and TA in a trans, trans configuration are in a face-to-face orientation and the dihedral angle between acid TA and base bib components is 9.5°. And the bib and TA ligands are joined together by two water molecules through hydrogen bonds between the carboxy oxygen atom in TA and the nitrogen atom of –C=N– in bib to give a macrocycle O1W–H1WB···O2W, O2W—H2WB···O1, O1W—H1WA···O2, N2—H2C···O1W and O2–H2D···N1 with the hydrogen bond geometry given in Table 1, and a face-to-face intracyclic \<i>p-\<i>p interaction at 3.69 Å (Fig. 1). Each bib group also features another macrocycles, resulting in 1-D chains running along the a axis. As illustrated in Fig. 2, the adjacent TA ligands are furthermore linked in the antiparallel alignment with offset along the ab plane by hydrogen bonds between the water molecules and the oxygen of TA groups (O2W—H2WA···O1, O1W—H1WA···O2, O2W—H2WB···O1, and O1W—H1WB···O2W (see Table 1). These ab planes are packed and stabilized by the hydrogen bonds between the lattice water and oxygen atom of TA ligands (O2w—H2wa···O1 = 2.82 Å) into a 3-D structure. Weak intermolecular C—H···O contacts contribute to the stability of the layered structure (Table 1).

Experimental

All the reagents and solvents employed were commercially available and used as received without further purification.

Syntheses of bib 1,4-Benzenedicarboxylic acid (2.31 g, 13.9 mmol), ethylenediamine (3.70 ml, 50 mmol), ethylenediamine dihydrochloride(6.64 g, 50 mmol) and toluene-p-sulfonic acid (0.208 g, 1.09 mmol) were added to the solvent of ethyleneglycol (20 ml), and the mixture solution was refluxed for 3 hr. About half of the ethylene glycol solvent was then slowly removed by distillation. The residue was dissolved in a mixture of water (40 ml) and concentrated HCl (11 M, 3 ml). The addition of 50% aqueous NaOH gave a yellow precipitate that was purified by recrystallization. The ligand bib was obtained in 83% based on 1,4-benzenedicarboxylic acid (ca 2.50 g). Found: C 66.98; H 6.92; N 26.08%. Calc. for C12H14N4: C 67.27; H 6.59; N 26.15%. Main IR bonds (KBr, cm-1): 3188m, 2936m, 2866m, 1606 s, 1532 s, 1466 s, 1345m, 1270 s, 1191w, 1080w, 981m, 907w, 767w, 687m.

Syntheses of bib.TA.4H2O (I) To a solution of bib (0.043 g, 0.2 mmol) in MeOH (15 ml), an aqueous solution (5 ml) of TA (0.034 g, 0.2 mmol) was added. The solution was allowed at room temperature in air for 48 hr by slow evaporation. Large colourless prismatic crystals of bib.TA.4H2O were obtained, which were collected by filtration, washed with water and dried in vacuum desiccator over silica gel (0.052 g, 56%). Found: C 53.02; H 6.20; N 12.31%. Calc. for C10H14N2O4: C 53.09; H 6.24; N 12.38%. Main IR bonds (KBr,cm-1): 3351m, 3142m, 2985m, 1626 s, 1601 s, 1582 s, 1516w, 1366 s, 1351 s, 1281m, 1040w, 864w, 822m, 752w, 689m.

Refinement

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(C or N). The positions of H atoms for water molecules were calculated (Nardelli, 1999) and included in the subsequent refinement as riding with Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Symmetry-related atoms shown labelled A and B. [symmetry codes A: (-x + 1, -y + 2, -z); B: (-x + 1, -y + 1, -z).
Fig. 2.
A partial packing diagram for the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H14N4·C8H6O4·4H2OF(000) = 480
Mr = 452.46Dx = 1.407 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.9929 (13) ÅCell parameters from 978 reflections
b = 16.847 (3) Åθ = 2.4–22.2°
c = 7.9615 (12) ŵ = 0.11 mm1
β = 94.899 (3)°T = 273 K
V = 1068.2 (3) Å3Block, colorless
Z = 20.50 × 0.35 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer2300 independent reflections
Radiation source: fine-focus sealed tube832 reflections with I > 2σ(I)
graphiteRint = 0.075
[var phi] and ω scansθmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −10→10
Tmin = 0.947, Tmax = 0.968k = −21→21
5588 measured reflectionsl = −5→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.090H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.257w = 1/[σ2(Fo2) + (0.1628P)2] where P = (Fo2 + 2Fc2)/3
S = 0.79(Δ/σ)max < 0.001
2300 reflectionsΔρmax = 0.71 e Å3
158 parametersΔρmin = −0.43 e Å3
6 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.12 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
N10.2209 (4)0.83842 (17)0.1428 (4)0.0622 (10)
N20.0932 (4)0.95122 (17)0.1837 (4)0.0621 (10)
H2C0.07441.00150.17970.074*
C1−0.0182 (6)0.8931 (2)0.2516 (6)0.0704 (13)
H1A−0.13180.89810.19910.085*
H1B−0.01990.89890.37260.085*
C20.0597 (6)0.8138 (2)0.2069 (6)0.0692 (13)
H2A0.07850.78000.30530.083*
H2B−0.01090.78600.12080.083*
C30.2264 (5)0.9167 (2)0.1292 (4)0.0558 (11)
C40.3678 (5)0.9588 (2)0.0625 (4)0.0541 (11)
C50.4927 (6)0.9183 (2)−0.0102 (5)0.0684 (13)
H50.48860.8632−0.01770.082*
O10.4731 (4)0.71811 (16)0.0453 (4)0.0702 (9)
O20.2324 (5)0.66542 (18)0.1033 (4)0.0915 (11)
H2D0.21100.71240.11830.137*
C60.3758 (6)1.0410 (2)0.0723 (5)0.0659 (12)
H60.29211.06890.12120.079*
C70.3793 (7)0.6590 (2)0.0620 (5)0.0649 (12)
C80.4386 (5)0.5771 (2)0.0299 (5)0.0570 (11)
C90.6008 (6)0.5648 (2)−0.0226 (5)0.0647 (12)
H90.66940.6082−0.03910.078*
C100.3416 (6)0.5107 (2)0.0509 (5)0.0644 (12)
H100.23390.51700.08490.077*
O1W0.9737 (5)0.61448 (19)0.2736 (5)0.0901 (12)
H1WA1.053 (4)0.627 (2)0.212 (5)0.11 (2)*
H1WB0.904 (5)0.6509 (19)0.296 (6)0.10 (2)*
O2W0.7204 (4)0.76340 (18)0.8161 (5)0.0821 (11)
H2WA0.64590.76910.73410.098*
H2WB0.700 (6)0.776 (7)0.916 (3)0.31 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.076 (2)0.0398 (17)0.073 (2)−0.0058 (16)0.0184 (18)0.0054 (15)
N20.074 (2)0.0401 (18)0.074 (2)0.0037 (17)0.0201 (19)0.0008 (15)
C10.082 (3)0.050 (2)0.082 (3)−0.003 (2)0.021 (2)0.002 (2)
C20.087 (3)0.047 (2)0.076 (3)−0.002 (2)0.022 (2)0.0008 (19)
C30.078 (3)0.040 (2)0.050 (2)0.000 (2)0.007 (2)0.0006 (16)
C40.072 (3)0.043 (2)0.048 (2)−0.0032 (19)0.015 (2)0.0032 (16)
C50.094 (3)0.039 (2)0.077 (3)0.003 (2)0.033 (3)−0.003 (2)
O10.089 (2)0.0440 (15)0.080 (2)0.0001 (15)0.0227 (16)−0.0008 (13)
O20.099 (3)0.0495 (17)0.132 (3)0.0123 (16)0.046 (2)−0.0028 (16)
C60.079 (3)0.042 (2)0.081 (3)0.004 (2)0.029 (2)0.0007 (19)
C70.080 (3)0.050 (2)0.067 (3)0.003 (2)0.018 (2)0.0043 (19)
C80.069 (3)0.047 (2)0.056 (2)0.0062 (19)0.012 (2)0.0006 (17)
C90.082 (3)0.042 (2)0.071 (3)−0.007 (2)0.011 (2)−0.0018 (19)
C100.080 (3)0.040 (2)0.075 (3)−0.0062 (19)0.020 (2)−0.0006 (18)
O1W0.100 (3)0.0528 (19)0.123 (3)−0.0071 (19)0.038 (2)0.0076 (17)
O2W0.076 (2)0.077 (2)0.094 (3)0.0043 (16)0.0140 (17)0.0025 (18)

Geometric parameters (Å, °)

N1—C31.324 (5)O2—C71.251 (5)
N1—C21.485 (5)O2—H2D0.8200
N2—C31.319 (5)C6—C5i1.381 (5)
N2—C11.458 (5)C6—H60.9300
N2—H2C0.8600C7—C81.487 (6)
C1—C21.528 (5)C8—C101.379 (5)
C1—H1A0.9700C8—C91.412 (6)
C1—H1B0.9700C9—C10ii1.377 (5)
C2—H2A0.9700C9—H90.9300
C2—H2B0.9700C10—C9ii1.377 (5)
C3—C41.472 (6)C10—H100.9300
C4—C51.377 (5)O1W—H1WA0.86 (3)
C4—C61.389 (5)O1W—H1WB0.86 (4)
C5—C6i1.381 (5)O2W—H2WA0.85
C5—H50.9299O2W—H2WB0.85 (4)
O1—C71.260 (5)
C3—N1—C2110.0 (3)C4—C5—C6i120.4 (3)
C3—N2—C1111.2 (3)C4—C5—H5119.9
C3—N2—H2C124.4C6i—C5—H5119.7
C1—N2—H2C124.4C7—O2—H2D109.5
N2—C1—C2103.1 (3)C5i—C6—C4120.5 (4)
N2—C1—H1A111.1C5i—C6—H6119.7
C2—C1—H1A111.1C4—C6—H6119.8
N2—C1—H1B111.1O2—C7—O1122.7 (4)
C2—C1—H1B111.1O2—C7—C8116.4 (4)
H1A—C1—H1B109.1O1—C7—C8120.9 (4)
N1—C2—C1102.7 (3)C10—C8—C9117.1 (3)
N1—C2—H2A111.2C10—C8—C7122.8 (4)
C1—C2—H2A111.2C9—C8—C7120.1 (4)
N1—C2—H2B111.2C10ii—C9—C8120.9 (4)
C1—C2—H2B111.2C10ii—C9—H9119.6
H2A—C2—H2B109.1C8—C9—H9119.5
N2—C3—N1112.3 (4)C9ii—C10—C8122.0 (4)
N2—C3—C4124.9 (3)C9ii—C10—H10118.8
N1—C3—C4122.8 (4)C8—C10—H10119.1
C5—C4—C6119.1 (4)H1WA—O1W—H1WB118 (2)
C5—C4—C3121.3 (3)H2WA—O2W—H2WB120.8
C6—C4—C3119.6 (4)
C3—N2—C1—C2−7.5 (4)C3—C4—C5—C6i179.9 (4)
C3—N1—C2—C1−7.6 (4)C5—C4—C6—C5i−0.1 (7)
N2—C1—C2—N18.6 (4)C3—C4—C6—C5i−179.9 (4)
C1—N2—C3—N12.9 (5)O2—C7—C8—C10−2.8 (6)
C1—N2—C3—C4−176.3 (4)O1—C7—C8—C10178.3 (4)
C2—N1—C3—N23.3 (5)O2—C7—C8—C9177.9 (4)
C2—N1—C3—C4−177.5 (3)O1—C7—C8—C9−1.0 (6)
N2—C3—C4—C5−172.2 (4)C10—C8—C9—C10ii−0.1 (6)
N1—C3—C4—C58.6 (6)C7—C8—C9—C10ii179.2 (4)
N2—C3—C4—C67.6 (6)C9—C8—C10—C9ii0.1 (6)
N1—C3—C4—C6−171.6 (4)C7—C8—C10—C9ii−179.2 (4)
C6—C4—C5—C6i0.1 (7)

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2W—H2WB···O1iii0.85 (4)2.37 (6)2.904 (5)121 (7)
O2W—H2WA···O1iv0.851.962.815 (5)180
O1W—H1WB···O2Wv0.85 (4)2.08 (4)2.926 (5)172 (5)
O1W—H1WA···O2vi0.86 (3)1.85 (2)2.707 (5)172 (3)
O2—H2D···N10.822.132.934 (4)165
N2—H2C···O1Wvii0.861.982.828 (4)167
C5—H5···O10.932.503.407 (4)165
C6—H6···O1Wvii0.932.473.380 (6)166

Symmetry codes: (iii) x, y, z+1; (iv) x, −y+3/2, z+1/2; (v) x, −y+3/2, z−1/2; (vi) x+1, y, z; (vii) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2204).

References

  • Bruker (1998). SMART, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Jeffrey, G. A. (1997). An introduction to Hydrogen Bonding New York: Oxford University Press.
  • Nardelli, M. (1999). J. Appl. Cryst.32, 563–571.
  • Ren, C.-X., Cheng, L., Ye, B.-H. & Chen, X.-M. (2007). Inorg. Chim. Acta, 360, 3741–3747.
  • Ren, C.-X., Li, S.-Y., Yin, Z.-Z., Lu, X. & Ding, Y.-Q. (2009). Acta Cryst. E65, m572–m573. [PMC free article] [PubMed]
  • Shang, S.-M., Ren, C.-X., Wang, X., Lu, L.-D. & Yang, X.-J. (2009). Acta Cryst. E65, o2221–o2222. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Thaimattam, R., Reddy, D. S., Xue, F., Mak, T. C. W., Nangia, A. & Desiraju, G. R. (1998). J. Chem. Soc. Perkin Trans. 2, pp. 1783–1789.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography